JP2005292276A - Radiation sensitive composition, laminate and method for manufacturing the same, and electronic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation sensitive composition forming a resin film excellent in sensitivity to radiation and excellent also in uniformity of film thickness, rough part planarizing property, heat-resistant shape retentivity and dielectric characteristics, and to provide a laminate obtained by stacking on a substrate a resin film comprising the radiation sensitive composition, uniform in coating film thickness, and excellent in rough part planarizing property. <P>SOLUTION: The radiation sensitive composition comprises a cycloolefin-base polymer having a protonic polar group, a crosslinking agent, a radiation sensitive compound and a solvent, wherein the crosslinking agent is a polyfunctional epoxy compound having ≥3 epoxy groups and the solvent is a mixed solvent consisting of a polyalkylene glycol compound and a nitrogen-containing solvent. The laminate consists of the substrate and the resin film formed thereon using the radiation sensitive composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a radiation-sensitive composition and a laminate having a resin film obtained from the radiation-sensitive composition on a substrate, and more specifically, suitable for manufacturing electronic components such as display elements, integrated circuit elements, and solid-state imaging elements. A radiation-sensitive composition, a laminate having a resin film obtained from the radiation-sensitive composition on a substrate, a method for producing the laminate, and an electronic component comprising the laminate.

For electronic parts such as display elements, integrated circuit elements, solid-state image sensors, color filters, black matrices, etc., protective films to prevent deterioration and damage, flattening films to flatten the element surface and wiring, electrical Various resin films are provided as an electrical insulating film or the like for maintaining insulation. In addition, a resin film as an interlayer insulating film is provided in an element such as a thin film transistor type liquid crystal display element or an integrated circuit element in order to insulate between wirings arranged in layers. Such a resin film is required to have various properties such as insulation, heat resistance, transparency, water absorption resistance, and chemical resistance.
Recently, in such an electronic component, multilayer wiring has been performed, so that a high degree of insulation between each layer can be maintained and a resin film having sufficient unevenness flatness can be formed. The material is required.

For this reason, a radiation sensitive resin composition containing an alkali-soluble cyclic olefin resin containing an ester group, a quinonediazide compound, and a crosslinking agent such as methylolmelamine has been proposed (Patent Document 1). However, although the resin film obtained using this radiation-sensitive resin composition has excellent properties as an insulating film such as low dielectric constant, heat resistance, unevenness flatness, transparency, and solvent resistance, When viewed as a whole, it was found that the thickness of the formed resin film was not necessarily uniform, and there was a problem in storage stability such as polymer deposition during storage.
Patent Document 2 discloses a radiation-sensitive resin composition comprising a resin having an alicyclic skeleton and alkali-soluble by the action of an acid, a radiation-sensitive acid generator, and a specific solvent. The present invention seeks to form a resist film having a uniform thickness by combining a specific resin and a specific solvent with excellent properties such as sensitivity, resolution, and developability, and particularly excellent transparency to radiation. It is.
The present applicant is a radiation-sensitive resin composition comprising an alicyclic olefin resin, an acid generator, a crosslinking agent, and a solvent, wherein the solvent contains at least a specific glycol system. A radiation sensitive resin composition was proposed (Patent Document 3).
Further, the present applicant is a radiation-sensitive resin composition comprising an alicyclic olefin resin, an acid generator, a crosslinking agent and a solvent, wherein the solvent is a mixed solvent comprising at least two different solvents, and The radiation sensitive resin composition characterized by 5 to 40 weight% of this mixed solvent being the aprotic polar solvent containing a nitrogen atom or a sulfur atom was proposed (patent document 4).

  However, with these radiation-sensitive compositions, higher performance required for radiation-sensitive compositions with the recent reduction in size, thickness, and performance of devices, specifically, a uniform resin film thickness is formed. , Unevenness flatness and heat-resistant shape retention may not be sufficiently satisfied. There is also a need for improved sensitivity to radiation.

Japanese Patent Laid-Open No. 10-307388 Japanese Patent Laid-Open No. 10-254139 JP 2003-156838 A JP 2003-195488 A

  The present invention was made in order to cope with the recent reduction in size and thickness of elements and improvement in safety, and is excellent in sensitivity to radiation, film thickness uniformity, unevenness flatness, heat resistant shape retention, It is an object of the present invention to provide a radiation-sensitive composition that forms a resin film having excellent dielectric properties, a laminate in which a resin film using the radiation-sensitive composition is formed on a substrate, and a method for producing the laminate. .

  As a result of intensive studies in order to solve the above-mentioned problems, the present inventors have made a radiation-sensitive composition comprising a cyclic olefin polymer containing a protic polar group, a crosslinking agent, a radiation-sensitive compound and a solvent. If a polyfunctional epoxy compound having three or more epoxy groups is used as a crosslinking agent, and a polyalkylene glycol compound solvent and a nitrogen-containing compound solvent are used as a solvent, the resin film is excellent in sensitivity to radiation. The inventors found that a radiation-sensitive composition having a uniform thickness and having excellent unevenness flatness, heat-resistant shape retention and dielectric properties can be obtained, and further research has been conducted based on these findings to complete the present invention. It was.

Thus, according to the present invention, a radiation-sensitive composition comprising a cyclic olefin polymer having a protic polar group, a crosslinking agent, a radiation-sensitive compound and a solvent, wherein the crosslinking agent has three or more epoxy groups. There is provided a radiation-sensitive composition comprising a polyfunctional epoxy compound having a polyalkylene glycol compound solvent and a nitrogen-containing solvent.
In the present invention, the cyclic olefin polymer having a protic polar group preferably contains 10 to 90% by weight of the protic polar group-containing cyclic olefin unit.
In the present invention, the polyalkylene glycol compound solvent is preferably a polyalkylene glycol in which both terminal hydroxyl groups are esterified or etherified.
Furthermore, in this invention, it is preferable to further contain the oxygen-containing compound solvent which does not contain a nitrogen atom as a solvent.
According to this invention, the laminated body formed by laminating | stacking the resin film which uses the said radiation sensitive composition on a board | substrate is also provided.
This laminate can be obtained by forming a resin film on a substrate using the radiation-sensitive composition and then crosslinking the resin as necessary.
In the present invention, the resin film may be a patterned resin film.
According to the present invention, a resin film is further formed on the substrate using the radiation-sensitive composition, and the resin film is irradiated with actinic radiation to form a latent image pattern in the resin film, and then developed on the resin film. The manufacturing method of the laminated body of Claim 6 which makes a latent image pattern actualize by making a liquid contact and forms a patterned resin film on a board | substrate.
Furthermore, in the method for producing a laminate of the present invention, a resin cross-linking reaction may be performed after a patterned resin film is formed on a substrate.
Furthermore, according to this invention, the electronic component which consists of the said laminated body is provided.

  The radiation-sensitive composition of the present invention can be applied to various applications because it provides a resin film that is excellent in sensitivity, resin film thickness uniformity and unevenness flattening property, and has extremely good dielectric properties and heat-resistant shape retention. Further, since the laminate of the present invention is excellent in the film thickness uniformity of the resin film, the unevenness flattening property, the dielectric property, and the heat-resistant shape retention property, for example, a display device, an integrated circuit device, a solid-state imaging device, a color filter , Protective film for elements such as black matrix, planarizing film for planarizing the element surface and wiring, insulating film for maintaining electric insulation (electric insulating film of thin transistor type liquid crystal display elements and integrated circuit elements) It is suitable as a material for electronic parts such as an interlayer insulating film, a solder resist film, etc.), a microlens, and a spacer.

  The radiation-sensitive composition of the present invention is a radiation-sensitive composition comprising a cyclic olefin polymer containing a protic polar group, a radiation-sensitive compound, a crosslinking agent and a solvent, , Using a specific compound.

In the cyclic olefin-based polymer containing a protic polar group used in the present invention, the protic polar group is a hetero atom, preferably an atom of Groups 15 and 16 of the periodic table, more preferably a periodic rule. It is an atomic group in which a hydrogen atom is directly bonded to an atom of Table 15 and Group 16 first and second period, particularly preferably an oxygen atom.
Specific examples of the protic polar group include polar groups having an oxygen atom such as carboxyl group (hydroxycarbonyl group), sulfonic acid group, phosphoric acid group, hydroxyl group; primary amino group, secondary amino group, A polar group having a nitrogen atom such as a primary amide group or a secondary amide group (imide group); a polar group having a sulfur atom such as a thiol group; Among these, those having an oxygen atom are preferable, and a carboxyl group is more preferable.

In the present invention, the number of protic polar groups contained in the cyclic olefin polymer containing a protic polar group is not particularly limited, and different types of protic polar groups may be contained.
In the present invention, the protic polar group contained in the cyclic olefin-based polymer containing a protic polar group may be bonded to the cyclic olefin monomer unit but may be bonded to a monomer unit other than the cyclic olefin monomer. Although it may couple | bond, it is desirable to couple | bond with the cyclic olefin monomer unit.

In the present invention, the cyclic olefin polymer constituting the portion other than the protic polar group of the cyclic olefin polymer containing a protic polar group (hereinafter sometimes referred to as “base portion”) is the cyclic olefin polymer. Any of a homopolymer and a copolymer, a copolymer of a cyclic olefin and another monomer may be used, or a hydrogenated product thereof may be used.
These cyclic olefin-based polymers containing a protic polar group can be used individually or in combination of two or more in different compositions.

  The cyclic olefin polymer containing a protic polar group used in the present invention is a polymer consisting only of monomer units derived from a cyclic olefin monomer (a) containing a protic polar group. Other monomer units that are copolymerizable with the monomer unit derived from the cyclic olefin monomer (a) containing a protic polar group and the cyclic olefin monomer (a) containing a protic polar group The copolymer which consists of a monomer unit induced | guided | derived from a body may be sufficient.

  In the cyclic olefin-based polymer containing a protic polar group used in the present invention, the ratio of a monomer unit containing a protic polar group to another monomer unit (a single unit containing a protic polar group). (Mer unit / other monomer unit) is usually in a range of 100/0 to 10/90, preferably 90/10 to 20/80, more preferably 80/20 to 30/70 in weight ratio. Selected to be.

Specific examples of the cyclic olefin monomer (a) containing a protic polar group include 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-hydroxycarbonylbicyclo [2]. 2.1] hept-2-ene, 5-carboxymethyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5-exo-6-endo-dihydroxycarbonylbicyclo [2.2. 1] hept-2-ene, 8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-exo-9-endo-dihydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . Carboxyl group-containing cyclic olefins such as 1 ^7,10 ] dodec-3-ene; 5- (4-hydroxyphenyl) bicyclo [2.2.1] hept-2-ene, 5-methyl-5- (4-hydroxy) Phenyl) bicyclo [2.2.1] hept-2-ene, 8- (4-hydroxyphenyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8- (4-hydroxyphenyl) tetracyclo [4.4.0.1 ^2,5 . And a hydroxy group-containing cyclic olefin such as ^{17, 10} ] dodec-3-ene. Among these, a carboxyl group-containing cyclic olefin is preferable. These protic polar group-containing cyclic olefins may be used alone or in combination of two or more.

As a monomer copolymerizable with the cyclic olefin monomer (a) containing a protic polar group, the cyclic olefin monomer (b) having a polar group other than the protic polar group has no polar group. There are no cyclic olefin monomers (sometimes referred to as “polar group-free cyclic olefin monomers”) (c), and monomers (d) other than cyclic olefins.
Among these, Preferably it is the cyclic olefin monomer (b) containing polar groups other than a protic polar group, and a polar group non-containing cyclic olefin monomer (c), More preferably, other than a protic polar group It is a cyclic olefin monomer (b) containing a polar group.

Specific examples of polar groups other than protic polar groups include ester groups (referred to generically as alkoxycarbonyl groups and aryloxycarbonyl groups), N-substituted imide groups, epoxy groups, halogen atoms, cyano groups, carbonyloxycarbonyls. Those having a group (an acid anhydride residue of a dicarboxylic acid), an alkoxy group, a carbonyl group, a tertiary amino group, a sulfone group, a halogen atom, an acryloyl group and the like are shown.
Of these, an ester group, an N-substituted imide group, and a cyano group are preferable, and an ester group and an N-substituted imide group are more preferable. In particular, an N-substituted imide group is preferable.

Examples of the ester group-containing cyclic olefin include 5-acetoxybicyclo [2.2.1] hept-2-ene, 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, and 5-methyl-5. -Methoxycarbonylbicyclo [2.2.1] hept-2-ene, 8-acetoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like.

Examples of the N-substituted imide group-containing cyclic olefin include N- (4-phenyl)-(5-norbornene-2,3-dicarboximide).
Examples of the cyano group-containing cyclic olefin include 8-cyanotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-cyanotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 5-cyanobicyclo [2.2.1] hept-2-ene, and the like.
Examples of the halogen atom-containing cyclic olefin include 8-chlorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-chlorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like.
These cyclic olefins having polar groups other than protic polar groups may be used alone or in combination of two or more.

Specific examples of the non-polar group-containing cyclic olefin monomer (c) include bicyclo [2.2.1] hept-2-ene (common name: norbornene), 5-ethyl-bicyclo [2.2.1]. Hept-2-ene, 5-butyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-methylidene-bicyclo [2. 2.1] hept-2-ene, 5-vinyl-bicyclo [2.2.1] hept-2-ene, tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (conventional name: dicyclopentadiene), tetracyclo ^{[8.4.0.1 11,14.} 0 ^3,7 ] pentadeca-3,5,7,12,11-pentaene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dec-3-ene (common name: tetracyclododecene), 8-methyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-vinyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-propenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-3,10-diene, cyclopentene, cyclopentadiene, 1,4-methano -1,4,4a, 5,10,10a hexa hydro anthracene, 8-phenyl - tetracyclo [4.4. 0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene), pentacyclo [7.4.0.1 ^{3 , 6} . 1 ^10,13 . 0 ^2,7] pentadeca-4,11-diene, pentacyclo [9.2.1.1 ^4,7. 0 ^2,10 . 0 ^3,8 ] pentadeca-5,12-diene and the like. These polar group-free cyclic olefin monomers (c) can be used alone or in combination of two or more.

  A typical example of the monomer (d) other than the cyclic olefin is a chain olefin. Examples of the chain olefin include ethylene; propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4- Methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, C2-C20 α-olefins such as 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; 1,4-hexadiene, 4-methyl-1 , 4-hexadiene, 5-methyl-1,4-hexadiene, non-conjugated dienes such as 1,7-octadiene, and the like. These monomers can be used alone or in combination of two or more.

As a preferred method for producing a cyclic olefin polymer containing a protic polar group used in the present invention, the cyclic olefin monomer (a) containing a protic polar group is polymerized and hydrogenated as necessary. Method.
If necessary, the cyclic olefin monomer (a) containing a protic polar group may be copolymerized with a monomer (the monomer (b), (c) or (d) described above). Can be copolymerized.

  In addition, the protic polar group-containing cyclic olefin polymer used in the present invention is introduced into the cyclic olefin polymer not containing a protic polar group by a known method after introducing a protic polar group, if necessary. It can also be obtained by a method of hydrogenation. Hydrogenation may be performed on the polymer before introduction of the protic polar group.

  In the method for producing the protic polar group-containing cyclic olefin polymer, the protic polar group may be a precursor, and the precursor is subjected to a chemical reaction such as decomposition by light or heat, hydrolysis, etc. What is necessary is just to convert into a group. For example, when the protic polar group is a carboxyl group, an ester group may be used instead of the protic polar group.

  The cyclic olefin polymer not containing a protic polar group can be obtained using the monomers (b) to (d). In this case, it goes without saying that a monomer containing a protic polar group may be used in combination.

  As a modifier for introducing a protic polar group, a compound having a carbon-carbon unsaturated bond reactive with a protic polar group in one molecule is usually used. Specific examples of such compounds include acrylic acid, methacrylic acid, angelic acid, tiglic acid, oleic acid, elaidic acid, erucic acid, brassic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, atropaic acid. Unsaturated carboxylic acids such as acid and cinnamic acid; allyl alcohol, methyl vinyl methanol, crotyl alcohol, methallyl alcohol, 1-phenylethen-1-ol, 2-propen-1-ol, 3-butene- 1-ol, 3-buten-2-ol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, 2- Such as methyl-3-buten-1-ol, 4-penten-1-ol, 4-methyl-4-penten-1-ol, 2-hexen-1-ol, etc. And the like can be given; saturated alcohols. The modification reaction may be carried out in accordance with a conventional method, and is usually performed in the presence of a radical generator.

The polymerization method of each monomer may be in accordance with a conventional method, for example, a ring-opening polymerization method or an addition polymerization method is employed.
As the polymerization catalyst, for example, metal complexes such as molybdenum, ruthenium and osmium are preferably used. These polymerization catalysts can be used alone or in combination of two or more. The amount of the polymerization catalyst is usually from 1: 100 to 1: 2,000,000, preferably from 1: 500 to 1: 1,000,000, more preferably in the molar ratio of metal compound to cyclic olefin in the polymerization catalyst. Is in the range of 1: 1,000 to 1: 500,000.

Hydrogenation of the polymer is usually performed using a hydrogenation catalyst.
As the hydrogenation catalyst, for example, those generally used for hydrogenation of olefin compounds can be used. Specifically, a Ziegler type homogeneous catalyst, a noble metal complex catalyst, a supported noble metal catalyst, and the like can be used. Among these hydrogenation catalysts, side reactions such as functional group modification do not occur, and noble metal complex catalysts such as rhodium and ruthenium can be used because carbon-carbon unsaturated bonds in the polymer can be selectively hydrogenated. A nitrogen-containing heterocyclic carbene compound or a ruthenium catalyst coordinated with a phosphine having a high electron donating property is particularly preferable.

The weight average molecular weight (Mw) of the cyclic olefin polymer containing a protic polar group used in the present invention is usually 1,000 to 1,000,000, preferably 1,500 to 100,000. Preferably it is the range of 2,000-10,000.
The molecular weight distribution of the cyclic olefin polymer containing a protic polar group used in the present invention is usually 4 or less, preferably 3 or less, and more preferably 3 or less in terms of weight average molecular weight / number average molecular weight (Mw / Mn) ratio. Is 2.5 or less.
The iodine value of the cyclic olefin polymer containing a protic polar group used in the present invention is usually 200 or less, preferably 50 or less, more preferably 10 or less. When the iodine value of the cyclic olefin polymer containing a protic polar group is in this range, it is particularly excellent in heat resistance and suitable.

The radiation-sensitive composition of the present invention is characterized by containing a polyfunctional epoxy compound having three or more epoxy groups as a crosslinking agent. The number of epoxy groups in the polyfunctional epoxy compound is preferably 3 to 100, more preferably 5 to 50, and most preferably 10 to 30. When the number of epoxy groups in the cross-linking agent is within this range, the radiation-sensitive composition is excellent in solubility in a solvent, and the film thickness uniformity of the formed resin film, unevenness flatness, heat resistance, It is excellent in properties such as heat-resistant shape retention and dielectric properties, and is suitable.
The polyfunctional epoxy compound preferably has an alicyclic structure, and more preferably has three or more epoxy groups bonded to the alicyclic structure portion directly or via a divalent linking group. It is an epoxy compound. The alicyclic structure may be obtained by hydrogenating an aromatic ring.
By using such a polyfunctional epoxy compound, characteristics such as sensitivity to radiation, uniformity of resin film thickness, flatness of uneven portions, heat-resistant shape retention and dielectric properties are highly balanced.

Examples of such epoxy compounds are hydrogenated bisphenol type epoxy resins, hydrogenated novolac type epoxy resins, glycidyl esters of alicyclic polyvalent carboxylic acids or epoxidized products of alicyclic olefins, and the like. The thing which has 3 or more can be mentioned.
Specific examples of such an epoxy compound include a trifunctional epoxy compound having a dicyclopentadiene skeleton (trade name “XD-1000” manufactured by Nippon Kayaku Co., Ltd.), [2,2-bis (hydroxymethyl) 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 1-butanol (a 15-functional alicyclic epoxy resin having a cyclohexane skeleton and a terminal epoxy group. Trade name “EHPE3150”, manufactured by Daicel Chemical Industries, Ltd. ), Epoxidized 3-cyclohexene-1,2-dicarboxylic acid bis (3-cyclohexenylmethyl) modified ε-caprolactone (aliphatic cyclic trifunctional epoxy resin, trade name “Epolide GT301”, manufactured by Daicel Chemical Industries, Ltd.) Epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ε-capro Lactone (aliphatic cyclic tetrafunctional epoxy resin. Trade name “Epolide GT401”, manufactured by Daicel Chemical Industries, Ltd.) can be mentioned.
In addition, as an epoxy compound having three or more epoxy groups having no alicyclic structure, an aromatic amine type polyfunctional epoxy compound (trade name “H-434”, manufactured by Tohto Kasei Kogyo Co., Ltd.), a cresol novolak type Functional epoxy compound (trade name “EOCN-1020”, manufactured by Nippon Kayaku Co., Ltd.), phenol novolac type polyfunctional epoxy compound (Epicoat 152, 154, manufactured by Japan Epoxy Resin Co., Ltd.), polyfunctional epoxy compound having a naphthalene skeleton (trade name) EXA-4700 (Dainippon Ink Chemical Co., Ltd.), chain alkyl polyfunctional epoxy compound (trade name “SR-TMP”, Sakamoto Yakuhin Kogyo Co., Ltd.), polyfunctional epoxy polybutadiene (trade name “Epolide PB3600”, Daicel Chemical) Manufactured by Kogyo Co., Ltd.), bisphenol A type polyfunctional epoxy resin (Epicoat 157S65, 57S70, manufactured by Japan Epoxy Resins), and the like.

The molecular weight of the polyfunctional epoxy compound having three or more epoxy groups used in the present invention is usually 500 to 50,000, preferably 1,000 to 10,000, more preferably 1,500 to 5,000, Most preferably, it is 2,000-4,000. When the molecular weight is in this range, the stability during heating and the gelation efficiency are highly balanced, which is preferable.
These polyfunctional epoxy compounds having three or more epoxy groups can be used alone or in combination of two or more, and the blending amount thereof is 100 parts by weight of the cyclic olefin polymer having the protic polar group. The amount is usually 1 to 200 parts by weight, preferably 10 to 100 parts by weight, and more preferably 20 to 50 parts by weight. When the amount used is in this range, the film thickness uniformity, unevenness flattening property and heat resistant shape retention property of the formed resin film are highly improved, which is preferable.

In the present invention, in addition to the polyfunctional epoxy compound having three or more epoxy groups, other crosslinking agents can be used in combination as necessary.
Other crosslinkers that can be used in combination are groups other than epoxy groups that can crosslink with protic polar groups of cyclic olefin polymers having 2 or less epoxy groups and / or protic polar groups (for example, amino groups, carboxyl groups). Group, a hydroxyl group, an isocyanate group, etc., preferably an amino group, an isocyanate group, and the like.) It is sufficient that they have a total of 2 or more, preferably 3 or more. It may be the same or different.
Examples of such a cross-linking agent include an epoxy compound having two epoxy groups, an epoxy compound having an alicyclic skeleton; an epoxy compound having two or more epoxy groups, a cresol novolak skeleton, a phenol novolak skeleton. , An epoxy compound having a bisphenol A skeleton or a naphthalene skeleton; and a trimethylolpropane type epoxy compound having two or more epoxy groups.

Specific examples of the crosslinking agent other than the epoxy compound include aliphatic polyamines such as hexamethylenediamine; aromatic polyamines such as 4,4′-diaminodiphenyl ether and diaminodiphenylsulfone; 2,6-bis (4 ′ -Azidobenzal) azides such as cyclohexanone and 4,4'-diazidodiphenylsulfone; polyamides such as nylon, polyhexamethylenediamine telelephthalamide, polyhexamethyleneisophthalamide; N, N, N ', N', N Melamines such as “, N”-(hexaalkoxymethyl) melamine; glycolurils such as N, N ′, N ″, N ″ ′-(tetraalkoxymethyl) glycoluril; ethylene glycol di (meth) acrylate, etc. Acrylate compound; hexamethylene diisocyanate polyiso Isocyanate compounds such as cyanate, isophorone diisocyanate polyisocyanate, tolylene diisocyanate polyisocyanate, hydrogenated diphenylmethane diisocyanate; 1,4-di- (hydroxymethyl) cyclohexane, 1,4-di- (hydroxymethyl) norbornane; 1 3,4-trihydroxycyclohexane.
These other crosslinking agents can be used alone or in combination of two or more.
The amount of the crosslinking agent used is appropriately selected according to the purpose of use, but is usually 1 to 200 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the cyclic olefin polymer having a protic polar group. More preferably, it is 20 to 50 parts by weight. When the amount used is in this range, the film thickness uniformity, unevenness flattening property and heat resistant shape retention property of the formed resin film are highly improved, which is preferable.

The radiation-sensitive compound used in the present invention is a compound that can absorb a radiation such as an ultraviolet ray or an electron beam and cause a chemical reaction, and also has a cyclic olefin-based heavy compound having a protic group used in the present invention. The alkali solubility of the coalescence can be controlled.
Examples of such radiation-sensitive compounds include azide compounds such as acetophenone compounds, triarylsulfonium salts, and quinonediazide compounds, with azide compounds being preferred, and quinonediazide compounds being particularly preferred.
As the quinonediazide compound, for example, an ester compound of a quinonediazidesulfonic acid halide and a compound having a phenolic hydroxyl group can be used.
Examples of the quinone diazide sulfonic acid halide include 1,2-naphthoquinone diazide-5-sulfonic acid chloride, 1,2-naphthoquinone diazide-4-sulfonic acid chloride, 1,2-benzoquinone diazide-5-sulfonic acid chloride, and the like.

Typical examples of the compound having a phenolic hydroxyl group include 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1. -[4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and the like.
Other compounds having a phenolic hydroxyl group include 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2-bis (4-hydroxyphenyl) propane, tris (4- Hydroxyphenyl) methane, 1,1,1-tris (4-hydroxy-3-methylphenyl) ethane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, novolak resin oligomer, phenolic hydroxyl group Examples thereof include oligomers obtained by copolymerizing one or more compounds and dicyclopentadiene.
These radiation sensitive compounds can be used alone or in combination of two or more.
The amount of the radiation-sensitive compound used is usually 1 to 100 parts by weight, preferably 5 to 50 parts by weight, and more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the cyclic olefin polymer containing a protic polar group. Part range. When the amount of the radiation sensitive compound used is within this range, when patterning the resin film formed on the substrate, the difference in solubility between the radiation irradiated part and the radiation non-irradiated part becomes large, and patterning by development is easy. In addition, the radiation sensitivity is also high, which is preferable.

The radiation-sensitive composition of the present invention is characterized in that the solvent comprises a polyalkylene glycol compound solvent and a nitrogen-containing compound solvent.
In the present invention, the polyalkylene glycol compound is a general term for a polyalkylene glycol having a plurality of alkylene glycol chains and one obtained by esterifying or etherifying either or both of the terminal hydroxyl groups of the polyalkylene glycol.
In the polyalkylene glycol compound solvent used in the present invention, the number of alkylene glycol chains is not particularly limited, but is usually 2 to 10, preferably 2 to 5, and more preferably 2. In addition, the polyalkylene glycol compound is preferably one in which at least one of the terminal hydroxyl groups is esterified or etherified, and more preferably one in which both terminal hydroxyl groups are esterified or etherified. From the viewpoint of availability and operability, the alkylene moiety preferably has 2 to 3 carbon atoms, particularly preferably 2 carbon atoms.

  Examples of the polyalkylene glycol compound solvent include polyalkylene glycols having hydroxyl groups at both ends, such as diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether , Dialkylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. Diethylene glycol monoacetate, dipropylene glycol Polyalkylene glycol monoesters in which one of terminal hydroxyl groups such as monoacetate is esterified; diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol ethyl methyl ether, dipropylene glycol diethyl ether, Polyalkylene glycol diethers in which both terminal hydroxyl groups are etherified, such as triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol diethyl ether, tripropylene glycol dimethyl ether, tripropylene glycol ethyl methyl ether, tripropylene glycol diethyl ether Kind; Polyalkylene glycol monoether esters in which the terminal hydroxyl groups of ester glycol ether monomethyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, etc. are esterified and etherified, respectively; diethylene glycol diacetate, dipropylene glycol diacetate And polyalkylene glycol diesters such as triethylene glycol diacetate;

Among these, polyalkylene glycol compounds in which both terminal hydroxyl groups are esterified or etherified are preferable, polyalkylene glycol compounds in which both terminal hydroxyl groups are etherified (that is, polyalkylene glycol diethers) are more preferable, Glycol diethers are most preferred.
These polyalkylene glycol compound solvents can be used alone or in combination of two or more.

Examples of the nitrogen-containing compound solvent used in the present invention include chain amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide; N-methyl-2- And cyclic amides such as pyrrolidone.
Among these, cyclic amides are preferable, and N-methyl-2-pyrrolidone is more preferable.
Use of these nitrogen-containing compound solvents is preferable because the photosensitivity of the resin film obtained using the radiation-sensitive composition is improved. These nitrogen-containing compound solvents can be used alone or in combination of two or more.
The ratio of the polyalkylene glycol compound solvent and the nitrogen-containing compound solvent is appropriately selected depending on the purpose of use, and is usually 95/5 to 5 in terms of the polyalkylene glycol compound solvent / nitrogen-containing compound solvent ratio (weight ratio). / 95, preferably 95/5 to 50/50, and more preferably 90/10 to 60/40.

The amount of the solvent used is usually 20 to 10,000 parts by weight, preferably 50 to 5,000 parts by weight, more preferably 100 parts per 100 parts by weight of the cyclic olefin polymer containing a protic polar group. It is the range of -1,000 weight part.
In the radiation-sensitive composition of the present invention, when an oxygen-containing compound solvent that does not contain a nitrogen atom is added to a mixed solvent of a polyalkylene glycol compound and a nitrogen-containing solvent, the resin film thickness uniformity and unevenness flatness are high. Therefore, it is preferable.

  Examples of the oxygen-containing compound solvent containing no nitrogen atom include alcohols such as methanol, ethanol, propanol, butanol and 3-methoxy-3-methylbutanol; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol, propylene glycol and the like Monoalkylene glycols such as ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and the like; ethylene glycol Monoalkylene glycol monoesters such as monoacetate and propylene glycol monoacetate Methyl cellosolve acetate (ethylene glycol methyl ether acetate), ethyl cellosolve acetate (ethylene glycol ethyl ether acetate), propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono n-propyl ether acetate, propylene glycol mono i-propyl Monoalkylene glycol ether esters such as ether acetate, propylene glycol mono n-butyl ether acetate, propylene glycol mono i-butyl ether acetate, propylene glycol mono sec-butyl ether acetate, propylene glycol mono t-butyl ether acetate;

Chain and cyclic ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2-pentanone; ethyl lactate, ethyl acetate, butyl acetate, ethyl 2-hydroxypropionate, 2-hydroxy-2- Methyl methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Examples include chain and cyclic esters such as ethyl ethoxypropionate, methyl 3-ethoxypropionate, and γ-butyrolactone; dimethyl sulfoxide; and the like.
Among these, monoalkylene glycol compounds such as monoalkylene glycols, monoalkylene glycol monoethers, monoalkylene glycol monoesters, monoalkylene glycol ether esters, and ketones are preferable.
These oxygen-containing solvent containing no nitrogen atom can be used alone or in combination of two or more. The blending amount is appropriately selected according to the purpose of use, but is usually 1 to 100 parts by weight, preferably 3 to 60 parts by weight, preferably 5 to 40 parts by weight based on 100 parts by weight of the polyalkylene glycol compound solvent. The range is parts by weight.

In the present invention, a solvent other than the polyalkylene glycol compound solvent, the nitrogen-containing compound solvent, and the oxygen-containing compound solvent not containing a nitrogen atom can be added.
Examples of the other solvent include aliphatic hydrocarbons such as hexane, heptane and octane: alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; It is done. These other solvents can be used singly or in combination of two or more, and the blending amount thereof is appropriately selected within a range not impairing the effects of the present invention.

The radiation-sensitive composition of the present invention may contain a resin component other than the cyclic olefin polymer containing a protic polar group, other compounding agents, and the like, if necessary.
Examples of other resin components include cyclic olefin polymers having no protic polar groups, styrene resins, vinyl chloride resins, acrylic resins, polyphenylene ether resins, polyarylene sulfide resins, polycarbonate resins, polyester resins. , Polyamide resin, polyethersulfone resin, polysulfone resin, polyimide resin, rubber and elastomer. These other resin components can be used alone or in combination of two or more, and the blending amount thereof is appropriately selected within a range not impairing the effects of the present invention.

Examples of other compounding agents include sensitizers, surfactants, latent acid generators, antioxidants, light stabilizers, adhesion aids, antistatic agents, antifoaming agents, pigments, dyes, and the like. Can do.
Examples of the sensitizer include 2H-pyrido- (3,2-b) -1,4-oxazin-3 (4H) -ones, 10H-pyrido- (3,2-b) -1,4- Preferred examples include benzothiazines, urazoles, hydantoins, barbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxans, maleimides and the like.
Surfactants are used for the purpose of preventing streaking and improving developability. For example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and other polyoxyethylenes are used. Ethylene alkyl ethers; polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; nonionic series such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate Surfactant; Fluorosurfactant; Silicone surfactant; (Meth) acrylic acid copolymer surfactant.

The latent acid generator is used for the purpose of improving the heat resistance and chemical resistance of the radiation-sensitive composition of the present invention. For example, the latent acid generator is a cationic polymerization catalyst that generates an acid by heating, such as a sulfonium salt, a benzothiazolium. Examples thereof include salts, ammonium salts, and phosphonium salts. Of these, sulfonium salts and benzothiazolium salts are preferred.
As the antioxidant, there can be used phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, lactone antioxidants and the like used in ordinary polymers. For example, as phenols, 2,6-di-t-butyl-4-methylphenol, p-methoxyphenol, styrenated phenol, n-octadecyl-3- (3 ′, 5′-di-t-butyl-4 '-Hydroxyphenyl) propionate, 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 2-t-butyl-6- (3'-t-butyl-5'-methyl-2' -Hydroxybenzyl) -4-methylphenyl acrylate, 4,4'-butylidene-bis- (3-methyl-6-tert-butylphenol), 4,4'-thio-bis (3-methyl-6-tert-butylphenol) ), Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], alkylated bisphenol, and the like. Examples of the phosphorus-based antioxidant include triphenyl phosphite and tris (nonylphenyl) phosphite. Examples of the sulfur-based antioxidant include dilauryl thiodipropionate. Among these, from the viewpoint of yellowing during heating, a phenol-based antioxidant is preferable, and among them, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] is preferable.

Light stabilizers include benzophenone-based, salicylic acid ester-based, benzotriazole-based, cyanoacrylate-based, metal complex salt-based ultraviolet absorbers, hindered amine-based (HALS), and the like that capture radicals generated by light. But you can. Among these, HALS is a compound having a piperidine structure and is preferable because it is less colored and has good stability with respect to the composition of the present invention. Specific compounds include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl 1,2,3,4 -Butanetetracarboxylate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like.
Examples of the adhesion assistant include functional silane coupling agents, and specific examples thereof include trimethoxysilyl benzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, Examples include γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.

The radiation-sensitive composition of the present invention comprises a cyclic olefin polymer containing a protic polar group, a radiation-sensitive compound and a crosslinking agent as essential components, and other components as necessary, and a polyalkylene glycol compound solvent and nitrogen. It can be produced by dispersing or dissolving in a mixed solvent containing the contained compound solvent as an essential component. Methods for dissolving or dispersing each component in the solvent may be in accordance with conventional methods, for example, stirring using a stirrer and a magnetic stirrer, high-speed homogenizer, dispersion, planetary stirrer, twin-screw stirrer, ball mill, three-roll Etc. can be used. The radiation-sensitive composition of the present invention is preferably used after being dissolved or dispersed in a solvent and then filtered using, for example, a filter having a pore size of about 0.5 μm.
The solid content concentration of the radiation-sensitive composition of the present invention is usually 1 to 70% by weight, preferably 5 to 50% by weight, more preferably 10 to 40% by weight. When the solid content concentration is in this range, it is excellent in the coating property on the substrate, the film thickness uniformity of the formed resin film, the unevenness flattening property, and the like.

The laminate of the present invention comprises a substrate and a resin film formed thereon using the radiation sensitive composition of the present invention.
In the present invention, for example, a printed wiring board, a silicon wafer substrate, a glass substrate, a plastic substrate, or the like can be used as the substrate. In addition, a glass substrate, a plastic substrate or the like used in the display field in which a thin transistor type liquid crystal display element, a color filter, a black matrix, or the like is formed is also preferably used.
The thickness of the resin film is usually in the range of 0.1 to 100 μm, preferably 0.5 to 50 μm, more preferably 0.5 to 30 μm.

The laminate of the present invention can be obtained by forming a resin film on a substrate using the radiation-sensitive composition of the present invention and then crosslinking the resin film as necessary.
The method for forming the resin film on the substrate is not particularly limited, and for example, a method such as a coating method or a film lamination method can be used. The coating method is, for example, a method in which a radiation-sensitive composition is coated on a substrate, then dried by heating to remove the solvent, and then cross-linked as necessary. Examples of the method for applying the radiation-sensitive composition on the substrate include various methods such as spraying, spin coating, roll coating, die coating, doctor blade method, spin coating, bar coating, and screen printing. Can be adopted. The heating and drying conditions vary depending on the type and blending ratio of each component, but are usually 30 to 150 ° C., preferably 60 to 120 ° C., usually 0.5 to 90 minutes, preferably 1 to 60 minutes, and more. Preferably it may be performed in 1 to 30 minutes.
In the film lamination method, for example, after applying the radiation-sensitive composition onto a substrate such as a resin film or a metal film, the solvent is removed by heat drying to obtain a B stage film, and then this B stage film is placed on the substrate. It is a method of laminating. The heating and drying conditions vary depending on the type and blending ratio of each component, but are usually 30 to 150 ° C., preferably 60 to 120 ° C., usually 0.5 to 90 minutes, preferably 1 to 60 minutes, and more. Preferably, it may be performed for 1 to 30 minutes. Film lamination can be performed using a pressure bonding machine such as a pressure laminator, a press, a vacuum laminator, a vacuum press, or a roll laminator.

In the present invention, the resin film may be a patterned resin film (hereinafter referred to as “patterned resin film”).
The laminate of the present invention, particularly a laminate in which a patterned resin film is formed on a substrate, is useful as various electronic components.
The resin film patterned on the substrate can be formed as follows.
First, the resin film formed on the substrate as described above is irradiated with actinic radiation to form a latent image having a desired pattern. The actinic radiation is not particularly limited as long as it can activate the radiation-sensitive compound and change the alkali solubility of the radiation-sensitive composition. Specifically, ultraviolet rays, ultraviolet rays having a single wavelength such as g-line or i-line, light rays such as KrF excimer laser light and ArF excimer laser light; particle beams such as electron beams; As a method for selectively irradiating these actinic radiations in a pattern to form a latent image pattern, a conventional method may be used. For example, ultraviolet, g-line, i-line, KrF excimer is used by a reduction projection exposure apparatus or the like. A method of irradiating a light beam such as a laser beam or an ArF excimer laser beam through a desired mask pattern, a method of drawing with a particle beam such as an electron beam, or the like can be used. When light is used as the active radiation, it may be single wavelength light or mixed wavelength light. Irradiation conditions may be appropriately selected depending on the active radiation to be used, for example, when using a light beam of wavelength 200 to 450 nm, the amount of irradiation is usually 10~1,000mJ / cm ^2, preferably 50 to 500 mJ / It is a range of cm ² and is determined according to irradiation time and illuminance. After irradiation with actinic radiation in this manner, the resin film is heat-treated at a temperature of about 60 to 130 ° C. for about 1 to 2 minutes as necessary.

  Next, the latent image pattern formed on the resin film is developed and made visible. In the present invention, such a process is called “patterning”, and the patterned resin film is called “patterned resin film”. As the developer, an aqueous solution of an alkaline compound is usually used. As the alkaline compound, for example, an alkali metal salt, an amine, or an ammonium salt can be used. The alkaline compound may be an inorganic compound or an organic compound. Specific examples of these compounds include alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate and sodium metasilicate; ammonia water; primary amines such as ethylamine and n-propylamine; diethylamine Secondary amines such as di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and choline Alcohol alcohols such as dimethylethanolamine and triethanolamine; pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] nona-5 -En, N-Me Cyclic amines such as Rupiroridon; and the like. These alkaline compounds can be used alone or in combination of two or more. As an aqueous medium of the alkaline aqueous solution, water; a water-soluble organic solvent such as methanol or ethanol can be used. The alkaline aqueous solution may have a surfactant added in an appropriate amount.

As a method of bringing the developer into contact with the resin film having the latent image pattern, for example, a paddle method, a spray method, a dipping method, or the like is used. The development is usually appropriately selected in the range of 0 to 100 ° C, preferably 5 to 55 ° C, more preferably 10 to 30 ° C, and usually 30 to 180 seconds.
After the desired patterned resin film is formed on the substrate in this way, the substrate is rinsed with a rinsing solution in order to remove development residues on the substrate, the back surface of the substrate, and the edge of the substrate, if necessary. Can do. After the rinse treatment, the remaining rinse liquid is removed with compressed air or compressed nitrogen.
Furthermore, if necessary, in order to deactivate the radiation-sensitive compound, the active radiation can be applied to the entire surface of the substrate having the patterned resin film. The method exemplified in the formation of the latent image pattern can be used. The resin film may be heated simultaneously with irradiation or after irradiation. Examples of the heating method include a method of heating the substrate in a hot plate or an oven. The temperature is usually in the range of 100 to 300 ° C, preferably 120 to 200 ° C.

  Crosslinking of the patterned resin film formed on the substrate may be appropriately selected depending on the type of the crosslinking agent, but is usually performed by heating. The heating method can be performed using, for example, a hot plate or an oven. The heating temperature is usually 180 to 250 ° C., and the heating time is appropriately selected depending on the size and thickness of the resin film and the equipment used. For example, when a hot plate is used, the oven is usually used for 5 to 60 minutes. When used, it is usually in the range of 30 to 90 minutes. Heating may be performed in an inert gas atmosphere as necessary. The inert gas is not particularly limited as long as it does not contain oxygen and does not oxidize the resin film. Examples thereof include nitrogen, argon, helium, neon, xenon, and krypton. Among these, nitrogen and argon are preferable, and nitrogen is particularly preferable. In particular, an inert gas having an oxygen content of 0.1% by volume or less, preferably 0.01% by volume or less, particularly nitrogen is suitable. These inert gases can be used alone or in combination of two or more.

Hereinafter, the present invention will be described in more detail with reference to synthesis examples and examples. In addition, the part and% in each example are mass references | standards unless there is particular notice.
Each characteristic was evaluated by the following method.
[Weight average molecular weight (Mw) and number average molecular weight (Mn) of polymer]
Using gel permeation chromatography (HLC-8020 manufactured by Tosoh Corporation), the molecular weight is calculated as polyisoprene equivalent molecular weight.
[Hydrogenation rate]
A hydrogenation rate is calculated | required as a ratio with respect to the carbon-carbon double bond mole number before hydrogenation of the hydrogenated carbon-carbon double bond mole number by < ¹ > H-NMR spectrum.
[Iodine number]
Measured according to JIS K0070B.

[In-plane film thickness uniformity of resin film]
After 50 ml of a radiation sensitive composition was dropped on a glass substrate with a low-reflection Cr film of 550 × 650 × 0.7 mm and spin-coated, it was dried on a hot plate at 95 ° C. for 2 minutes to give a film thickness of 3 μm. A coated substrate is formed. Using an optical interference type film thickness measuring device VM-8000J (Dainippon Screen Co., Ltd.), measure the film thickness of 25 points set at approximately equal intervals in 5 rows vertically and horizontally, with 10 mm inside from the periphery of the coated substrate as the effective measurement area. The in-plane film thickness fluctuation range is calculated by the following formula.
In-plane film thickness fluctuation width = 100 × (maximum film thickness value−minimum film thickness value) / (average film thickness)
The in-plane film thickness uniformity is determined according to the following criteria based on the numerical value of the in-plane film thickness fluctuation range.
◎: Less than 10 ○: 10 or more and less than 15 △: 15 or more and less than 20 ×: 20 or more

[Unevenness flatness]
Using a spinner (made by Mikasa Co., Ltd.) on a substrate in which an aluminum wiring having a grid pattern with a line width of 20 μm, a space of 300 μm, and a height of 1.5 μm is formed on a glass substrate of 300 × 350 × 0.7 mm, radiation sensitivity The composition is applied, dried using a hot plate at 95 ° C. for 120 seconds, and formed into a film having a dried film thickness (distance from the glass substrate) of 2.5 μm. Next, the film thickness (distance from the glass substrate) is measured using a contact-type film thickness meter P-10 (manufactured by Tencor). The difference in film thickness between the portion with and without the aluminum wiring is obtained by the following formula, and the determination is made according to the following criteria.
Difference in film thickness (%) = 100 × (film thickness in a part with wiring−film thickness in a part without wiring) / film thickness in a part without wiring ◎: film thickness difference is less than 5% ○: 5% or more and less than 10 Δ: 10% or more and less than 15% ×: 15% or more

[sensitivity]
After applying the radiation-sensitive composition on a silicon substrate using a spin coater (D-629, manufactured by Dainippon Screen), drying treatment was performed on a hot plate at 90 ° C. for 120 seconds to obtain an optical film thickness meter SM. The film is formed to be 2.5 μm when measured with −200 (manufactured by Tencor).
Using an exposure machine (PLA501F, manufactured by Canon Inc.) and an L-39 filter on this resin film, a 10 μm line part and a space part have a one-to-one mask with light having an optical intensity of 405 nm at 6 mW / cm ^2. Then, irradiation is performed for a predetermined time.
Next, after developing with a 0.3% by weight aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 100 seconds, a positive pattern is formed by rinsing with ultrapure water for 1 minute.
At this time, the exposure amount when the 10 μm space portion that has been exposed and developed is not resolved is used as the sensitivity value, and the sensitivity is determined based on the following criteria based on the exposure value.
◎: 300 mJ / cm ² or less ○: 500 mJ / cm ² or more and 300 mJ / cm ² or less Δ: 500 mJ / cm ² or more and 1000 mJ / cm ² or less ×: Greater than 1000 mJ / cm ²

[Heat-resistant shape retention of resin film]
A crosslinkable resin composition was applied onto a substrate in which an aluminum film having a step of 1.5 μm was formed on a 300 × 350 × 0.7 mm glass substrate using a spinner (manufactured by Mikasa), and a hot plate was used. It is used and dried at 95 ° C. for 120 seconds, and the film is formed so that the film thickness after drying is 2.5 μm. The entire surface of this film was irradiated with ultraviolet rays having a light intensity at 365 nm of 5 mW / cm ² in air for 60 seconds, and then the glass substrate on which this pattern was formed was heated at 160 ° C. for 2 minutes using a hot plate. First heat treatment is performed. The cross section of the obtained pattern is observed with an electron microscope, and the width a of the lower end of the pattern is measured. Next, the glass substrate subjected to the first heat treatment is subjected to the second heat treatment at 230 ° C. for 1 hour using a clean oven. The cross section of the pattern subjected to the second heat treatment is observed with an electron microscope, the shape of the upper end of the pattern is evaluated, and the lower end width b of the pattern is measured. The percentage (b / a) of the lower end width b of the pattern after the second heat treatment with respect to the lower end width a of the pattern after the first heat treatment is determined and determined according to the following criteria.
A: Roundness is not recognized at the upper end, and the above ratio is 110% or less.
○: The upper end is rounded, but the above ratio is 120% or less.
Δ: The upper end is rounded, and the above ratio exceeds 120%.
X: The pattern is completely melted and fused with the adjacent pattern.

[Dielectric properties of resin film]
After applying the radiation sensitive composition on the aluminum substrate using a spinner (manufactured by Mikasa Co., Ltd.), it was dried at 95 ° C. for 120 seconds on a hot plate, and a stylus type film thickness meter P-10 (manufactured by Tencor) ) To form a film so as to be 3 μm. This film was not exposed to light and developed by immersing in a 0.3% aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 100 seconds, followed by rinsing with ultrapure water for 1 minute, and then the entire surface of the resin film. The radiation sensitive compound is deactivated by irradiation with ultraviolet rays having a light intensity at 365 nm of 5 mW / cm ² . Then, it heats with a 230 degreeC hotplate for 1 hour. An aluminum film having a thickness of 0.3 μm is formed on the resin film, and a dielectric constant of 1 MHz is measured in an environment at 23 ° C. Based on this dielectric constant, the following criteria are used for determination.
○: Dielectric constant is less than 3.
X: Dielectric constant is 3 or more.

[Synthesis Example 1]
8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene 60 parts, N-phenyl- (5-norbornene-2,3-dicarboximide) 40 parts, 1-hexene 1.3 parts, 1,3-dimethylimidazolidine-2 -0.05 part of ylidene (tricyclohexylphosphine) benzylidene ruthenium dichloride and 400 parts of tetrahydrofuran were charged into a pressure-resistant reactor made of nitrogen-substituted glass and reacted at 70 ° C for 2 hours with stirring to obtain a polymer solution A (solid content Concentration: about 20%).
A part of this polymer solution A is transferred to an autoclave equipped with a stirrer, and hydrogen is dissolved at a pressure of 4 MPa at 150 ° C. and reacted for 5 hours, and a polymer solution B containing a hydrogenated polymer (hydrogenation rate 100%). (Solid content concentration: about 20%) was obtained.
A heat-resistant container in which 1 part of activated carbon powder was added to 100 parts of the polymer solution B was placed in an autoclave, and hydrogen was dissolved at 150 ° C. under a pressure of 4 MPa for 3 hours while stirring. Next, the solution was taken out and filtered through a fluororesin filter having a pore size of 0.2 μm to separate the activated carbon to obtain a polymer solution. Filtration was performed without any delay. The polymer solution was poured into ethyl alcohol to solidify, and the produced crumb was dried to obtain a polymer. Mw of the obtained polymer in terms of polyisoprene was 5,500, and Mn was 3,200. The iodine value was 1.

[Example 1]
100 parts of the polymer obtained in Synthesis Example 1, a solvent having a total amount of 550 parts shown in Table 1, and 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1 as a 1,2-quinonediazide compound. -Methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.5 mol) condensate 25 parts by weight, alicyclic structure-containing polyfunctional as crosslinking agent 20 parts of an epoxy compound (molecular weight 2700, number of epoxy groups 15, EHPE 3150, manufactured by Daicel Chemical Industries, Ltd.), 1 part of γ-glycidoxypropyltrimethoxysilane as an adhesion aid and a silicone surfactant (manufactured by Shin-Etsu Chemical Co., Ltd., KP) -341) After mixing and dissolving 0.05 parts, the radiation sensitive composition was filtered through a polytetrafluoroethylene filter having a pore size of 0.45 μm. It was manufactured. About this radiation sensitive composition, the sensitivity, the resin film thickness uniformity, the unevenness flattening property, the heat resistant shape retention property, and the dielectric properties were evaluated. The results are shown in Table 1.

[Examples 2-3, Comparative Examples 1-2]
A radiation-sensitive composition was prepared in the same manner as in Example 1 except that the crosslinking agent and the solvent were changed as shown in Table 1. About these radiation sensitive compositions, the sensitivity, the resin film thickness uniformity, the unevenness flattening property, the heat resistant shape retaining property, and the dielectric properties were evaluated. The results are shown in Table 1.

[Footnotes in Table 1]
* 1 XD-1000: Epoxy compound (epoxy group number 3, molecular weight 714, alicyclic structure)
EXA-7015: Epoxy compound (epoxy group number 2, molecular weight 352, alicyclic structure)
* 2 EDM: Diethylene glycol ethyl methyl ether MAK: Methyl amyl ketone NMP: N-methyl-2-pyrrolidone PGPE: Propylene glycol monopropyl ether

From the results in Table 1, it can be seen that when a cross-linking agent having only two epoxy groups is used, the heat resistant shape retention is remarkably lowered and the sensitivity is also lowered (comparison between Example 1 and Comparative Example 1). . Moreover, even if it uses the crosslinking agent which has three epoxy groups, when a solvent does not satisfy the requirements of this invention, it turns out that it exists in the tendency which is inferior to a fall of a sensitivity, resin film thickness uniformity, and an uneven | corrugated | grooved part flatness. (Comparative example 2).
On the other hand, the radiation sensitive composition of the present invention provides a resin film excellent in film thickness uniformity, unevenness flattening property, heat resistant shape retention and dielectric properties, and in particular, a ketone compound in a mixed solvent. It can be seen that the above characteristics are particularly excellent when used in combination.

Claims (11)

A radiation-sensitive composition comprising a cyclic olefin polymer having a protic polar group, a crosslinking agent, a radiation-sensitive compound and a solvent, wherein the crosslinking agent is a polyfunctional epoxy compound having three or more epoxy groups. A radiation-sensitive composition, wherein the solvent comprises a polyalkylene glycol compound solvent and a nitrogen-containing compound solvent. The radiation-sensitive composition according to claim 1, wherein the cyclic olefin polymer having a protic polar group contains 10 to 90% by weight of the protic polar group-containing cyclic olefin unit. The radiation-sensitive composition according to claim 1 or 2, wherein the polyalkylene glycol compound solvent is a polyalkylene glycol in which hydroxyl groups at both terminals are esterified or etherified. The radiation-sensitive composition according to claim 1, further comprising an oxygen-containing compound solvent not containing a nitrogen atom as a solvent. A laminate comprising a substrate and a resin film formed thereon using the radiation-sensitive composition according to claim 1. The laminate according to claim 5, wherein the resin film is a patterned resin film. A method for producing a laminate comprising a substrate and a resin film formed thereon, wherein the resin film is formed on the substrate using the radiation-sensitive composition according to claim 1. . The manufacturing method of the laminated body of Claim 7 which bridge | crosslinks resin after forming a resin film on a board | substrate. A resin film is formed on a substrate using the radiation-sensitive composition according to claim 1, and the resin film is irradiated with actinic radiation to form a latent image pattern in the resin film, and then the resin The manufacturing method of the laminated body of Claim 6 which makes a latent image pattern actualize by making a developing solution contact a film | membrane, and forms a patterned resin film on a board | substrate. The manufacturing method of the laminated body of Claim 8 which performs the crosslinking reaction of resin after forming a patterned resin film on a board | substrate. An electronic component comprising the laminate according to claim 5.